Carbonylation of C−N Bonds in Tertiary Amines Catalyzed by Low‐Valent Iron Catalysts

The first iron catalysts able to promote the formal insertion of CO into the C?N bond of amines are reported. Using low‐valent iron complexes, including K₂[Fe(CO)₄], amides are formed from aromatic and aliphatic amines, in the presence of an iodoalkane promoter. Inorganic Lewis acids, such as AlCl₃ and Nd(OTf)₃, have a positive influence on the catalytic activity of the iron salts, enabling the carbonylation at a low pressure of CO (6 to 8 bars).     

A Smart Photochromic Semiconductor: Breaking the Intrinsic Positive Relation Between Conductance and Temperature

Breaking the intrinsic rule of semiconductors that conductivity increases with increase of temperature and realizing a dramatic dropping of conductivity at high temperature may arouse new intriguing applications, such as circuit overload or over‐temperature protecting. This goal has now been achieved through T‐type electron‐transfer photochromism of one organic semiconductor assembled by intermolecular cation???π interactions. Conductivity of the viologen‐based model semiconductor (H₂bipy)(Hox)₂ (H₂bipy=4,4′‐bipyridin‐1,1′‐dium; ox=oxalate) increased by 2 orders of magnitude after photoinduced electron transfer (a record for photoswitchable organic semiconductors) and generation of radical cation???π interactions, and fell by approximately 81 % at 100 °C through reverse electron transfer and degeneration of the radical cation???π interactions. The model semiconductor has at least two different electron transfer pathways in the decoloration process.     

Dehydrogenative Silylation of Alkenes for the Synthesis of Substituted Allylsilanes by Photoredox,Hydrogen‐Atom Transfer,and Cobalt Catalysis

A synergistic catalytic method combining photoredox catalysis, hydrogen‐atom transfer, and proton‐reduction catalysis for the dehydrogenative silylation of alkenes was developed. With this approach, a highly concise route to substituted allylsilanes has been achieved under very mild reaction conditions without using oxidants. This transformation features good to excellent yields, operational simplicity, and high atom economy. Based on control experiments, a possible reaction mechanism is proposed.     

Modulation versus Templating: Fine‐Tuning of Hierarchally Porous PCN‐250 Using Fatty Acids To Engineer Guest Adsorption

Modulation and templating are two synthetic techniques that have garnered significant attention over the last several years for the preparation of hierarchically porous metal–organic frameworks (HP‐MOFs). In this study, by using fatty acids with different lengths and concentrations as dual‐functional modulators/templates, we were able to obtain HP‐MOFs with tunable mesopores that exhibit different pore diameters and locations. We found that the length and concentration of the fatty acids can determine if micelle formation occurs, which in turn dictates the porosity of the resulting HP‐MOFs. The HP‐MOFs with different mesopores differed in their performance in gas uptake and dye adsorption, and the structure–performance relationships were ascribed to the pore diameters and locations. This approach could provide a potentially universal method to efficiently introduce hierarchal mesopores into existing microporous MOF adsorbents with tunable properties.     

Cover Picture: A Stepwise Annulation for the Transformation of Cyclic Ketones to Fused 6 and 7‐Membered Cyclic Enimines and Enones (Chin. J. Chem. 4/2019)

The cover picture shows a typical building within the Campus of Xiamen University displaying Chen Jiageng (Tan Kah Kee)'s style. Just like many beautiful buildings designed and constructed by human, Nature “designs and constructs” a huge number of useful molecules with fascinating structures called natural products. Many natural products possess a fused six or seven‐membered carbocyclic unity. On page 315–322, the Huang's group disclosed a three‐step “[2+n]” annulation method for the construction of fused six and seven‐membered carbocyclic enimines and enones. The method starts from simple cyclic ketones and terminal olefinic amides, and relies on both the Suzuki coupling reaction and the olefin‐amide based Friedel‐Crafts type acylating reaction, a method developed by Huang and coworkers.

     

Inside Cover: From Reactivity and Regioselectivity to Stereoselectivity: An Odyssey of Designing PIP Amine and Related Directing Groups for C—H Activation (Chin. J. Chem. 7/2019)

The inside cover picture shows the journey of developing PIP amine directing group for C—H activation, from controlling the reactivity and diastereoselectivity to enantioselectivity. In the presence of Pd or base metal catalysts, PIP amine enabled the activation of inert C—H bonds to form diverse C—C and C—heteroatom bonds. Its tuneable structure has triggered the design of chiral auxiliaries for diastereoselective C—H activation. More recently, enantioselective activation of unbiased methylene C—H bonds has been achieved by cooperative effects between PIP amine and axial chiral ligands. More details are discussed in the article by Shi et al. on page 647–656.

     

Preparation of graphene platelet-Ru(phen) 3 2+ assemblies and their application in electrochemiluminescence detection

Graphene platelet (GP)-Ru(phen) ₃ ²⁺ assembles have been prepared through self-assembly of poly sodium styrenesulfonate (PSS) functionalized GPs and Ru(phen) ₃ ²⁺ driven by electrostatic attraction interactions in aqueous solution. The resultant assembled GP-Ru(phen) ₃ ²⁺ hybrid structure modified electrode exhibits excellent electrochemiluminescence (ECL) behaviors because of the ECL active species Ru(phen) ₃ ²⁺ contained therein.     

Syntheses, structures and magnetic properties of three Co(II) coordination architectures based on a flexible multidentate carboxylate ligand and different N-donor ligands

Three new cobalt complexes, {[Co₅(tci)₂(bimb)₃(µ₃-O)₂(H₂O)₂]·3DMF·4H₂O} _n (1), {[Co₃(tci)₂(bib)]·2DMF·2H₂O} _n (2) and {[Co(Htci)(bpea)_0.5]·H₂O} _n (3) (H₃tci = tris(2-carboxyethyl)isocyanurate, bimb = 4,4′-bis(imidazol-1-yl)biphenyl, bib = 1,4-bis(imidazol-1-yl)benzene, bpea = 1,2-bis(4-pyridyl)ethane, DMF = N,N′-dimethylformamide), have been successfully synthesized through the assembly of Co(II) ions, H₃tci and different N-donor ligands, respectively. All complexes were structurally characterized by single crystal X-ray diffraction, elemental analyses, IR spectra, thermogravimetric (TG) analyses and X-ray powder diffraction (XRPD). Complex 1 exhibits a 3D three-fold parallel interpenetrated 3D → 3D structure with (6⁵·8) CdSO₄ topology. Complex 2 is built from [Co₃(µ₂-O_carboxyl)₂(CO₂)₄] clusters and linear bib ligands, displaying a two-fold parallel interpenetrated (3,8)-connected (4³)₂(4⁶·6¹⁸·8⁴) topology, while complex 3 is a 3D pillar-layered structure involving an infinite -Co-(µ₂-Ocarboxyl)(CO₂)-Co-chain. The diverse structures of the three complexes indicate that the skeletons of different N-donor ligands play an important role in the assembly of such different frameworks. In addition, magnetic investigation indicates that besides spin-orbit coupling of Co(II) ions, there exist antiferromagnetic exchange interactions in Co₅ and Co₃ clusters of 1 and 2, respectively.     

MgO Nanoparticles as a Recyclable Heterogeneous Catalyst for the Synthesis of Polyhydroquinoline Derivatives under Solvent Free Conditions

Magnesium oxide nanopartticels in average size between 35–120 nm were prepared by sonochemistry method. Synthesis of polyhydroquinoline derivatives using MgO nanoparticles from the reaction of dimedone, benzaldehyde, ethyl acetoacetate and ammonium acetate under solvent‐free conditions is reported. Easy handling, reusability, thermal stability and non‐toxicity of the catalyst make the present protocol as an eco‐friendly and economically acceptable method for synthesis of these heterocycles.